EP1035760B1 - Interlaminar insulating adhesive for multilayer printed circuit board - Google Patents

Interlaminar insulating adhesive for multilayer printed circuit board Download PDF

Info

Publication number
EP1035760B1
EP1035760B1 EP00104843A EP00104843A EP1035760B1 EP 1035760 B1 EP1035760 B1 EP 1035760B1 EP 00104843 A EP00104843 A EP 00104843A EP 00104843 A EP00104843 A EP 00104843A EP 1035760 B1 EP1035760 B1 EP 1035760B1
Authority
EP
European Patent Office
Prior art keywords
type epoxy
epoxy resins
printed circuit
component
multilayer printed
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP00104843A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1035760A3 (en
EP1035760A2 (en
Inventor
Toshio c/o Sumitomo Bakelite Co. Ltd. Komiyatani
Masao c/o Sumitomo Bakelite Co. Ltd. Uesaka
Masataka c/o Sumitomo Bakelite Co. Ltd. Arai
Hitoshi c/o Sumitomo Bakelite Co. Ltd. Kawaguchi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Bakelite Co Ltd
Original Assignee
Sumitomo Bakelite Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Bakelite Co Ltd filed Critical Sumitomo Bakelite Co Ltd
Publication of EP1035760A2 publication Critical patent/EP1035760A2/en
Publication of EP1035760A3 publication Critical patent/EP1035760A3/en
Application granted granted Critical
Publication of EP1035760B1 publication Critical patent/EP1035760B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J181/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Adhesives based on polysulfones; Adhesives based on derivatives of such polymers
    • C09J181/06—Polysulfones; Polyethersulfones
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4652—Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern
    • H05K3/4655—Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern by using a laminate characterized by the insulating layer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0333—Organic insulating material consisting of one material containing S
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/0129—Thermoplastic polymer, e.g. auto-adhesive layer; Shaping of thermoplastic polymer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0358—Resin coated copper [RCC]
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4652—Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S525/936—Encapsulated chemical agent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y10T428/31515—As intermediate layer
    • Y10T428/31522—Next to metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31511—Of epoxy ether
    • Y10T428/31529—Next to metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31533—Of polythioether

Definitions

  • the present invention relates to an interlaminar insulating resin adhesive for multilayer printed circuit board. More particularly, the present invention relates to an interlaminar insulating adhesive of epoxy resin type for multilayer printed circuit board, which has flame retardancy without containing halogen or phosphorus, which has excellent thermal property, which can give an interlaminar insulating layer of uniform thickness, and which is suitable for formation of fine pattern; as well as to a copper foil coated with said interlaminar insulating adhesive.
  • Production of a multilayer printed circuit board has been conducted by a process comprising steps of laminating, on an inner layer circuit substrate having a circuit, at least one prepreg obtained by impregnating a glass cloth with an epoxy resin, followed by semi-curing, laminating a copper foil thereon, and molding the resulting material into one piece by hot plate pressing.
  • the thickness variation of the interlaminar insulating resin layer after press molding tends to be large because the insulating resin layer contains no glass cloth as a base material; therefore, in such a case, it is necessary to employ strictly controlled molding conditions, making difficult the molding.
  • the interlaminar insulating adhesive is required to further have heat resistance and low thermal expansion coefficient so that the accuracy during circuit formation and component mounting can be maintained.
  • Many of interlaminar insulating adhesives of conventional type have a glass transition temperature of about 120°C and therefore give rise to delamination of insulating layer.
  • Thermosetting resins typified by epoxy resin, etc. are widely used, for their excellent properties, in printed circuit boards and other electric or electronic appliances. They are, in many cases, allowed to have flame retardancy so that they are resistant to fire. Flame retardancy of these resins has generally been achieved by using a halogen-containing compound (e.g. brominated epoxy resin as for example in JP-A-11 035 916). These halogen-containing compounds have high flame retardancy, but have various problems.
  • a halogen-containing compound e.g. brominated epoxy resin as for example in JP-A-11 035 916.
  • brominated aromatic compounds release corrosive bromine or hydrogen bromide when heat-decomposed and, when decomposed in the presence of oxygen, may generate very toxic so-called dioxins such as polybromodibenzofuran and polydibromobenzoxin; further, disposal of bromine-containing waste materials is difficult.
  • dioxins such as polybromodibenzofuran and polydibromobenzoxin
  • disposal of bromine-containing waste materials is difficult.
  • phosphorus compounds and nitrogen compounds have recently been studied as a flame retardant replacing bromine-containing flame retardants.
  • phosphorus compounds there is a fear that when their wastes are used for land reclamation, they may dissolve in water and pollute rivers or soils.
  • the present invention provides a multilayer printed circuit board having a glass cloth-free insulating layer, which has excellent thermal property and which is low in thickness variation of the interlaminar insulating resin layer.
  • the present invention lies in an interlaminar insulating adhesive for multilayer printed circuit board containing the following components as essential components:
  • the component (a) i.e. the sulfur-containing thermoplastic resin having a weight-average molecular weight of 10 3 to 10 5 is used so that (1) the resin flowability during press molding becomes low and the insulating layer formed can maintain an intended thickness, (2) the adhesive composition can have flexibility, and (3) the insulating resin layer can have improved heat resistance and reduced heat history.
  • the weight-average molecular weight is smaller than 10 3 , the flowability during molding is too high and the insulating layer formed is unable to maintain an intended thickness.
  • the component (a) has low compatibility with the epoxy resins and shows inferior flowability.
  • the weight-average molecular weight of the component (a) is preferably 5x10 3 to 10 5 from the standpoint of the flowability.
  • the sulfur-containing thermoplastic resin as component (a) is preferably amorphous because no crystal is formed when subjected to heat history of heating and cooling.
  • the component (a) preferably includes polysulfone and polyethersulfone.
  • the sulfur-containing thermoplastic resin when modified with a hydroxyl group, a carboxyl group or an amino group at the terminal(s), has high reactivity with the epoxy resins; as a result, the phase separation between the sulfur-containing thermoplastic resin and the epoxy resins after heat-curing can be suppressed, and the cured material has increased heat resistance.
  • a sulfur-containing thermoplastic resin modified as above is preferred.
  • the proportion of the high-molecular, sulfur-containing thermoplastic resin (a) is preferably 20 to 70% by weight based on the total resin.
  • the proportion is smaller than 20% by weight, the adhesive composition has no sufficiently high viscosity and is unable to reliably give an intended layer thickness; therefore, the insulating layer after pressing is unable to have a desired thickness, the outer-layer circuit is inferior in flatness, and heat resistance is insufficient.
  • the proportion of the sulfur-containing thermoplastic resin (a) is larger than 70% by weight, the adhesive composition is hard and lacks in elasticity; therefore, is inferior in adaptability and adhesion to the uneven surface of an inner layer circuit substrate during press molding, generating voids.
  • the component (b) i.e. the sulfur-containing epoxy or phenoxy resin having a weight-average molecular weight of 10 3 to 10 5 is added for adjustment of flowability, better handling, higher tenacity of cured material, etc.
  • the sulfur-containing epoxy or phenoxy resin there are ordinarily used bisphenol S type epoxy or phenoxy resin, and epoxy or phenoxy resin having both a bisphenol S skeleton and a bisphenol or biphenyl skeleton.
  • An epoxy or phenoxy resin having both a bisphenol S skeleton and a biphenyl skeleton is preferred because it has good compatibility with the component (a), and it preferably has a weight-average molecular weight of 10 4 to 10 5 from the standpoint of flowability. Owing to the presence of sulfur in the component (b), the component (b) can have good compatibility with the component (a), the resulting adhesive varnish can have stability, and the cured material can have uniformity and good thermal property.
  • the proportion of the component (b) used is ordinarily 10 to 40% by weight based on the total resin. When the proportion is smaller than 10% by weight, the flowability during press molding is not sufficient, the adhesion of the resulting adhesive is low; and voids are generated easily. Meanwhile, a proportion larger than 40% by weight tends to give insufficient heat resistance.
  • the component (c) i.e. the multifunctional epoxy resin having an epoxy equivalent of 500 or less is added.
  • the polyfunctional epoxy resin preferably has a weight-average molecular weight of 1,000 or less. The proportion of this component is 10 to 70% by weight based on the total resin. When the proportion is smaller than 10% by weight, the above effect is not obtained sufficiently. When the proportion is larger than 70% by weight, the effect of the high-molecular, sulfur-containing thermoplastic resin is small.
  • the epoxy resin as component (c) includes bisphenol type epoxy resin, novolac type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, alcohol type epoxy resin, alicyclic type epoxy resin, aminophenol type epoxy resin, etc.; when flame retardancy is needed, includes naphthalene type epoxy resin, biphenyl type epoxy resin, bisphenol S type epoxy resin, indene-modified phenolic novolac type epoxy resin, indene-modified cresol novolac type epoxy resin, phenyl ether type epoxy resin, phenyl sulfide type epoxy resin, etc., which are all superior in flame retardancy. These epoxy resins are high in proportion of aromatic ring and are superior in flame retardancy and heat resistance.
  • the component (d), i.e. the epoxy-curing agent includes amine compounds, imidazole compounds, acid anhydrides, etc. and there is no particular restriction as to the kind. However, an amine type curing agent having sulfone group is preferred.
  • the presence of sulfone group in the curing agent (d) enhances the compatibility between the thermoplastic resin (a) having sulfone group and the components (b) and (c), gives a uniform cured material, and enables formation of a stable insulating resin layer. Further, owing to the enhanced compatibility, better dielectric property, particularly smaller dielectric loss is possible, and higher storage stability, that is, storage stability of 3 months or longer at 20°C can be obtained.
  • the proportion of the curing agent is preferably 0.9 to 1.1 in terms of equivalent ratio to the total of the component (b) and the component (c). When the proportion deviates from this range, heat resistance and electrical property decrease.
  • Imidazole compounds can cure an epoxy resin sufficiently even when used in a small amount.
  • the imidazole compounds can allow the epoxy resin to effectively exhibit the flame retardancy.
  • a particularly preferred imidazole compound is one which has a melting point of 130°C or higher, is a solid at ordinary temperature, has low solubility in an epoxy resin, and quickly reacts with the epoxy resin at high temperatures of 150°C or more.
  • imidazole compound examples include 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-mehtylimidazole, bis(2-ethyl-4-methyl-imidazole), 2-phenyl-4-methyl-5-hydrxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole and triazine-added imidazoles.
  • These imidazoles are uniformly dispersible in an epoxy resin varnish, in the form of a fine powder.
  • Such an imidazole has low compatibility with an epoxy resin; therefore, no reaction takes place at ordinary temperature to 100°C and good storage stability can be obtained. When heated to 150°C or higher during molding under heat and pressure, the imidazole reacts with the epoxy resin, producing a uniform cured material.
  • acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride and the like; amine complexes of boron trifluoride; dicyandiamide or derivatives thereof; and so forth. Epoxy adducts or microencapsulated products of the above compounds can also be used.
  • a component reactive with the epoxy resin or the curing agent is possible to further use.
  • a component reactive with the epoxy resin or the curing agent examples include epoxy reactive diluents (e.g. monofunctional: phenyl glycidyl ether, bifunctional: resorcin diglycidyl ether and ethylene glycol glycidyl ether, trifunctional: glycerol triglycidyl ether), resole type or novolac type phenolic resins, and isocyanate compounds.
  • inorganic fillers such as fused silica, crystalline silica, calcium carbonate, aluminum hydroxide, alumina, clay, barium sulfate, mica, talc, white carbon, E glass fine powder and the like.
  • the proportion of the filler used is ordinarily 40% by weight or smaller based on the resin content. When the proportion is larger than 40% by weight, the viscosity of the interlaminar insulating resin is high and the flowability of the resin into the inner-layer circuit is low.
  • silane coupling agent e.g. epoxy silane
  • titanate type coupling agent for higher adhesion to copper foil or inner-layer circuit substrate or for higher moisture resistance
  • an antifoaming agent for prevention of void generation
  • a flame retardant of liquid or fine powder type e.g. flame retardant of liquid or fine powder type
  • the solvent used in the present adhesive it is necessary to select a solvent which does not remain in the adhesive after the adhesive has been coated on a copper foil and dried at 80 to 130°C.
  • a solvent which does not remain in the adhesive after the adhesive has been coated on a copper foil and dried at 80 to 130°C.
  • MEK methyl ethyl ketone
  • DMF dimethylformamide
  • the copper foil as defined in claim 10, coated with an interlaminar insulating adhesive according to the present invention is produced by coating an adhesive varnish which is obtained by dissolving individual adhesive components in a particular solvent at given concentrations, on the anchorage side of a copper foil, followed by drying at 80 to 130°C so that the concentration of volatile component in the adhesive becomes 4.0% or less, preferably 3.0 to 1.5%.
  • the thickness of the adhesive is preferably 100 ⁇ m or less. When the thickness exceeds 100 ⁇ m, variation in thickness appears and no uniform insulating layer is secured.
  • the adhesive layer When in the copper foil coated with an interlaminar insulating adhesive, the adhesive layer is formed in two layers of different flowability and the adhesive layer adjacent to the copper foil has lower flowability than the outer adhesive layer, excellent moldability is obtained and there can be produced a multilayer printed circuit board which has no void and which is low in variation in thickness of the interlaminar insulating layer.
  • the copper foil coated with an interlaminar insulating adhesive is laminated on an inner-layer circuit substrate by using an ordinary vacuum press or laminator, followed by curing, whereby a multilayer printed circuit board having an outer-layer circuit can be produced easily.
  • part refers to “part by weight”.
  • the adhesive varnish was coated on the anchorage surface of a copper foil of 18 ⁇ m in thickness by using a comma coater, followed by drying at 170°C for 5 minutes, to obtain a copper foil coated with an insulating adhesive in a thickness of 40 ⁇ m.
  • On the adhesive layer was coated the same adhesive varnish by using a comma coater, followed by drying at 150°C for 5 minutes, to newly form an insulating adhesive layer of 40 ⁇ m in thickness.
  • the surface of each copper foil of the inner-layer circuit sheet was subjected to a blackening treatment.
  • thermoplastic resin modified with hydroxyl group was converted to a non-modified amorphous polysulfone (weight-average molecular weight: 26,000), whereby multilayer printed circuit boards were produced.
  • TMA thermo mechanical analyzer
  • the presence or absence of voids between circuits and in clearance holes was examined visually.
  • Variation in thickness of insulating layer on inner-layer circuit was observed by sectional observation.
  • the sites of observation were (1) line (circuit) of fine circuit and (2) line (copper foil) between slits, of inner-layer circuit sheet.
  • the thickness of insulating layer was measured at the above observation sites for 5 samples, the average of 5 measurements was calculated for each site, and the difference between the two averages was taken as variation in insulating layer thickness.
  • V-0 and V-1 are the levels of combustibility specified by UL-94 specification.
  • the V-0 and V-1 shown in Table 1 indicate that these levels are met by individual samples.
  • V-0 refers to lower combustibility, i.e. higher flame retardancy than V-1.
  • the interlaminar insulating adhesive for multilayer printed circuit board according to the present invention has flame retardancy without containing any halogen or phosphorus, has excellent heat resistance without containing glass cloth, is low in variation in insulating layer thickness between circuit layers, and is suitable for formation of fine pattern; therefore, a multilayer printed circuit board can be easily produced using the above adhesive.
EP00104843A 1999-03-11 2000-03-07 Interlaminar insulating adhesive for multilayer printed circuit board Expired - Lifetime EP1035760B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP6425199 1999-03-11
JP6425199 1999-03-11

Publications (3)

Publication Number Publication Date
EP1035760A2 EP1035760A2 (en) 2000-09-13
EP1035760A3 EP1035760A3 (en) 2001-12-12
EP1035760B1 true EP1035760B1 (en) 2004-12-22

Family

ID=13252773

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00104843A Expired - Lifetime EP1035760B1 (en) 1999-03-11 2000-03-07 Interlaminar insulating adhesive for multilayer printed circuit board

Country Status (7)

Country Link
US (1) US6447915B1 (ko)
EP (1) EP1035760B1 (ko)
KR (1) KR100632169B1 (ko)
CN (1) CN1170908C (ko)
DE (1) DE60016823T2 (ko)
ES (1) ES2233232T3 (ko)
TW (1) TW491016B (ko)

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4423779B2 (ja) * 1999-10-13 2010-03-03 味の素株式会社 エポキシ樹脂組成物並びに該組成物を用いた接着フィルム及びプリプレグ、及びこれらを用いた多層プリント配線板及びその製造法
JP3485513B2 (ja) * 2000-01-19 2004-01-13 沖電気工業株式会社 半導体装置の製造方法
KR100315158B1 (ko) * 2000-08-02 2001-11-26 윤덕용 비솔더 플립 칩 본딩용 고신뢰성 비전도성 접착제 및 이를이용한 플립 칩 본딩 방법
US7370982B2 (en) * 2002-10-02 2008-05-13 Gentex Corporation Environmentally improved rearview mirror assemblies
US6899437B2 (en) * 2002-10-02 2005-05-31 Gentax Corporation Environmentally improved rearview mirror assembly
JP3949676B2 (ja) * 2003-07-22 2007-07-25 三井金属鉱業株式会社 極薄接着剤層付銅箔及びその極薄接着剤層付銅箔の製造方法
TW200533692A (en) * 2003-11-06 2005-10-16 Showa Denko Kk Curable polyester having an oxetanyl group at end and process for preparing the same, resist composition, jet printing ink composition, curing methods and uses thereof
JP5085125B2 (ja) * 2004-03-29 2012-11-28 住友ベークライト株式会社 樹脂組成物、樹脂付き金属箔、基材付き絶縁シートおよび多層プリント配線板
JP4829766B2 (ja) * 2006-12-13 2011-12-07 横浜ゴム株式会社 繊維強化複合材料用エポキシ樹脂組成物
CN101928538B (zh) * 2010-08-30 2012-12-26 黑龙江省科学院石油化学研究院 含聚砜低聚物热固化环氧树脂胶粘剂及其制备方法
US9068040B2 (en) * 2010-10-12 2015-06-30 Hexcel Corporation Solvent resistant thermoplastic toughened epoxy
CN102898779B (zh) * 2011-06-01 2015-05-27 深圳光启高等理工研究院 复合材料和基于复合材料制备基材的方法
CN102796346A (zh) * 2011-06-01 2012-11-28 深圳光启高等理工研究院 改性环氧树脂和基于改性环氧树脂制备基材的方法
CN105949716B (zh) * 2011-11-29 2019-01-04 三菱化学株式会社 环氧树脂组合物、预浸料以及纤维强化复合材料
DE112012006529T5 (de) * 2012-06-15 2015-03-12 Mitsubishi Electric Corporation Flüssige, wärmeaushärtende Harzzusammensetzung zum Isolieren einer Statorspule einer drehenden elektrischen Maschine, drehende elektrische Maschine, die diese verwendet, und Herstellungsverfahren dafür
CN103724944A (zh) * 2013-12-31 2014-04-16 广东生益科技股份有限公司 一种无卤环氧树脂组合物及其用途
US9867284B2 (en) * 2014-08-05 2018-01-09 At & S Austria Technologie & Systemtechnii Warpage control with intermediate material
US10886506B2 (en) * 2015-03-30 2021-01-05 Dai Nippon Printing Co., Ltd. Cell packaging material, method for manufacturing same, and cell
JP6174287B1 (ja) * 2015-11-24 2017-08-02 日東シンコー株式会社 樹脂組成物および電気絶縁シート
CN108676533B (zh) * 2018-05-03 2021-05-11 广东生益科技股份有限公司 树脂组合物及其制作的涂树脂铜箔
CN113897163B (zh) * 2021-12-09 2022-03-11 武汉市三选科技有限公司 一种粘接剂、芯片键合膜及其制备方法
CN115109387B (zh) * 2022-07-11 2023-09-22 陕西生益科技有限公司 一种树脂组合物及其应用

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4661559A (en) * 1983-05-20 1987-04-28 Union Carbide Corporation Impact resistant matrix resins for advanced composites
JPS60243113A (ja) 1984-05-17 1985-12-03 Sumitomo Chem Co Ltd 強靭性に優れたエポキシ樹脂組成物
KR920014611A (ko) 1991-01-22 1992-08-25 베르너 발데크 가요성 적층물 및 그의 제조방법
EP0498766A3 (en) 1991-02-04 1992-11-04 Ciba-Geigy Ag Modified polyarylenethers
GB2259812B (en) 1991-09-06 1996-04-24 Toa Gosei Chem Ind Method for making multilayer printed circuit board having blind holes and resin-coated copper foil used for the method
DE4217509A1 (de) 1992-05-27 1993-12-02 Basf Ag Epoxidharzmischungen
DE69323129T2 (de) 1992-08-11 1999-08-19 Hexcel Corp Mit Sulfonpolymeren zäher gemachte hitzehärtbare Harze
TW305860B (ko) * 1994-03-15 1997-05-21 Toray Industries
JP3669663B2 (ja) 1997-07-18 2005-07-13 住友ベークライト株式会社 多層プリント配線板用層間絶縁接着剤
JP4423779B2 (ja) * 1999-10-13 2010-03-03 味の素株式会社 エポキシ樹脂組成物並びに該組成物を用いた接着フィルム及びプリプレグ、及びこれらを用いた多層プリント配線板及びその製造法

Also Published As

Publication number Publication date
CN1170908C (zh) 2004-10-13
KR100632169B1 (ko) 2006-10-11
DE60016823D1 (de) 2005-01-27
DE60016823T2 (de) 2005-12-08
EP1035760A3 (en) 2001-12-12
KR20000062822A (ko) 2000-10-25
TW491016B (en) 2002-06-11
CN1267696A (zh) 2000-09-27
EP1035760A2 (en) 2000-09-13
US6447915B1 (en) 2002-09-10
ES2233232T3 (es) 2005-06-16

Similar Documents

Publication Publication Date Title
EP1035760B1 (en) Interlaminar insulating adhesive for multilayer printed circuit board
JP5387872B2 (ja) エポキシ樹脂組成物及びその硬化物
CN108485182B (zh) 一种高频树脂组合物及使用其制作的半固化片和层压板
JP4723865B2 (ja) 難燃性エポキシ樹脂組成物、同組成物を含有するプリプレグ、積層板およびプリント配線板
JP2007308640A (ja) 積層板用樹脂組成物、有機基材プリプレグ、金属張積層板およびプリント配線板
JP2007211182A (ja) 樹脂組成物、プリプレグ、積層板、金属張積層板およびプリント配線板
KR20140027493A (ko) 프리프레그, 적층판, 반도체 패키지 및 적층판의 제조 방법
JP5811974B2 (ja) ワニス、プリプレグ、樹脂付きフィルム、金属箔張積層板、プリント配線板
JP2003073543A (ja) 樹脂組成物、プリプレグ及びそれを用いたプリント配線板
KR100523913B1 (ko) 동박 부착 접착시트용 조성물 및 이를 이용한 동박 부착접착시트의 제조방법
JP3669663B2 (ja) 多層プリント配線板用層間絶縁接着剤
JP4337204B2 (ja) 多層プリント配線板用層間絶縁接着剤
JP2005209489A (ja) 絶縁シート
JP4070926B2 (ja) 多層プリント配線板用層間絶縁接着剤
EP1142953A1 (en) Cyanate-epoxy resin composition, and prepreg, metal foil-laminated plate and printed wiring board using the same
JPH08323916A (ja) 銅張樹脂複合材料
JP2833433B2 (ja) 積層板用エポキシ樹脂組成物および積層板の製造法
JP7352799B2 (ja) 樹脂組成物、プリプレグ、樹脂付きフィルム、樹脂付き金属箔、金属張積層板、及びプリント配線板
JPH11181124A (ja) プリプレグ
JP2003096296A (ja) 樹脂組成物、プリプレグ及びそれを用いたプリント配線板
JP3703143B2 (ja) 多層プリント配線板用層間絶縁接着剤および多層プリント配線板用層間絶縁接着剤付き銅箔
JP3632823B2 (ja) 多層プリント配線板用層間絶縁接着剤
JP2001089733A (ja) 多層プリント配線板用絶縁樹脂接着剤
JP3546594B2 (ja) エポキシ樹脂組成物、プリプレグ及び積層板
JPH08151507A (ja) 積層板用エポキシ樹脂組成物

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): DE ES FR GB IT

Kind code of ref document: A2

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17P Request for examination filed

Effective date: 20020516

AKX Designation fees paid

Free format text: DE ES FR GB IT

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE ES FR GB IT

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 60016823

Country of ref document: DE

Date of ref document: 20050127

Kind code of ref document: P

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2233232

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20050923

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20090304

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20090401

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20090306

Year of fee payment: 10

Ref country code: IT

Payment date: 20090317

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20090316

Year of fee payment: 10

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20100307

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20101130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20101001

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100307

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100307

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20110415

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110404

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100308